Multiautoclave with Set of Vessels for Combinatorial Synthesis of Zeolites and Other Materials

ABSTRACT

A vessel arrangement having a base and multiple vessels suited for simultaneously conducting a plurality of isolated experimental reactions or treatments at atmospheric process conditions or elevated temperatures and pressure condition has been developed. A component of a first material is introduced into one independent vessel through an opening in its top of the first vessel and another component of a second material is introduced into a different independent vessel through its top. Both vessels are removably located about a base at different first locations. Transformation of the components in the vessels then occurs to produce different materials therein. After completion of the experiments a displacement medium simultaneously urges the vessels from their respective locations about the base for discard or reuse after any necessary cleaning. Typically at least one property of the materials from the vessels is determined either within the vessel or after recovery of the materials.

CROSS REFERENCE TO THE APPLICATION

This application is a Division of copending application Ser. No.10/834,648 filed Apr. 29, 2004, the contents of which are herebyincorporated by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to a vessel arrangement having a base andmultiple vessels suited for simultaneously conducting a plurality ofisolated experimental reactions or treatments at atmospheric processconditions or elevated temperatures and pressure condition.

BACKGROUND OF THE INVENTION

In recent years, new, automated methods for the systematic preparationof new compounds, so-called “combinatorial techniques” have beendeveloped. A wide variety of methodologies, tools and techniques wearthe label of combinatorial methods. Generally these methods seek toaccelerate the discovery of new materials and the application of new andknown materials to new uses by increasing the number and rapidity ofmaterial tests though reductions in the size of material samples. Aparticular type of combinatorial methods focuses on the creation and/oranalysis of arrays of materials at discrete locations on a substrate ofsome type. The substrates often comprise a base having regions definesby depressions, wells, walls of other structural means to separate theregions and keep the different materials in the arrays isolated forsynthesis and analysis.

The size of the materials samples in the regions are of necessity keptsmall to achieve the objective of such arrays in the combinatorialmethodology. Accordingly the diameter of the regions seldom exceeds 15mm and usually presents regions of much smaller size. The small size ofthese regions can pose contamination problems. Contamination whetherdetected or undetected can interfere with the usefulness of such arraysby corrupting the data obtained from the material samples therebyleading to false conclusions that waste time and resources. Consequentlyreuse of a substrate such as a base that receives material directly onits surface requires thorough cleaning and/or treatment to avoid thepresence of any contaminants from previous experiments. Since theregions are by definition small, intensive and thorough cleaning of thesmall areas can present a challenge. Moreover the composition of thesubstrate or base may exacerbate the problems. The use of easilymachinable or formable materials facilitates the manufacture of thesmall structures on the surface of the base that define the vast numberof small regions needed for such arrays. However easily machinable andformable materials are typically less susceptible to the harshconditions needed to get the contaminants out of the small regions.

It is already known to synthesize a multitude of material samples inarrays of small vessels. For example, it is known to produce variousmetal oxides in small vessels having the form of individual cruciblesretained by a base. The use of individual vessels allows their disposalor intensive cleaning once all experimental steps with the materialcontained therein are concluded. However, many of the synthesisoperations, treatments steps and analysis of a material may requiremovement of the arrays. So on one hand the vessels must remain fixed inthe base throughout such procedures that may in addition to movementbetween pieces of equipment require shaking stirring or agitation in theequipment. But at the same time the vessel must not become so fixed inthe base or substrate that they are not readily removed for disposal.Fitting vessels into a base with a tight tolerance may prevent theirremoval after completion of the experiment. Moreover, certain treatmentsteps may create minor distortion of the vessels or the base that bindsthem together by the completion of the experiment.

Such conditions occur in the synthesis of many materials. One example ofsuch materials, zeolites, are prepared by so-called hydrothermalsynthesis at temperatures ranging from 100° C. to 200° C. requiringcrystallization times of one hour or more. For syntheses being carriedout at temperatures that are higher than the boiling point of thesolvent, it is necessary to use pressure vessels, and these have to besuitable for the temperature and pressure used during the operation.This further requires the sealing of the vessels in a manner thatprevents contamination between the materials undergoing synthesis.

Zeolite syntheses are usually performed in strongly alkaline media,often at pH>14, and the reaction mixture will often contain toxicchemicals such as, e.g., fluoride. Conventionally, syntheses that may beperformed at temperatures lower than 110° C. are carried out in polymerbottles, often Teflon™ (tetrafluoroethylene), while reactions at highertemperatures require steel autoclaves, perhaps lined with Teflon™.Having a cost effective combinatorial method for such syntheses is quiteuseful since he price of an autoclave of this type with the requiredsafety details is typically of the order of about 1,000 United Statesdollars or higher. Furthermore, such an autoclave will weigh from 1kilogram and upwards, and all of these elements represent limitationsregarding the number of syntheses that may be performed in mostlaboratories in the course of one year.

Zeolite synthesis is often carried out by keeping the synthesis mixtureat around 100° C. for at least 6 h. At these moderate temperaturessealed chambers are necessary in order to avoid drying out of thesynthesis mixture. US 3,130,007 A exemplifies conventional zeolitesynthesis. Common to all the synthesis procedures mentioned and for allother known synthesis procedures for the preparation of zeolites on alaboratory scale with the purpose of discovering new zeolites or tooptimize existing zeolites is that these are performed in a cumbersomeand expensive manner by having to separately prepare each reactionmixture, which typically consists of 4-7 reagents, and by adding thereagents one by one. In many other examples the is synthesis of zeolitesand other molecular sieves needs temperatures well above 100° C., sothat steel pressure vessels or the like are required.

New, combinatorial techniques which may be used for liquid phasesynthesis at temperatures above approximately 100° C. have beendisclosed in WO 02/07873 that provides the synthesis to be performed ina hermetically sealed vessel at elevated pressures. There is, e.g., aknown design called “multiblock”, see Krchnak, V.; Vagner, J. PeptideRes. 1990, 3,182, consisting of i) a Teflon™ block holding 42 reactors,polypropylene syringes equipped with polymer filters, ii) a vacuumadapter connecting each reactor to a vacuum line (not described indetail) which enables rapid washing in an apparatus for continuous flow,iii) two Teflon™ plates with 42 stoppers to which the Teflon™ block isfastened during use, and iv) a glass cover used during homogenization.The problem with this design is that the reactors which are made ofglass and which do not have protected sidewalls may be used only at lowpressures and not in strongly alkaline solutions.

Until recently there has been no available literature describing methodsor equipment for using arrays that might be used for practical work tosufficiently retain vessels in the array to perform combinatorialexperimentation while providing facile withdrawal of the vessels forreplacement in the substrate or base. Zeolite synthesis can beparticularly problematic inasmuch as such syntheses almost withoutexception require hydrothermal treatment of a solution or gel with arelatively high content of water and often high contents of organiccompounds in a closed chamber under elevated temperatures and highpressure.

WO 98/36826 discloses a system for screening of synthesis conditions forthe preparation of zeolites and other non-carbon materials requiringhydrothermal conditions in the temperature range of 100° C. to 250° C.Some of the parameters that have been made more cost efficient with themultiautoclave of WO 98/36826 include: reduced size of the separatereaction chambers and increased number of reaction chambers; reduced useof reactants; automated addition of reactants, for instance by apipetting machine which makes quick and exact addition of all liquidreactants possible; and devices allowing automated analysis with X-raydiffraction and automatic identification of known crystalline phases. WO98/36826 has also disclosed automated equipment for larger synthesisseries and preparation formulations based on mixtures of differentliquids/solutions with varying reactant ratios.

The WO 98/36826 invention is a pressure and temperature reactor vesselcomprising a central block having a multitude of perforations. Theperforations are through-going perforations, cavities or other form ofholes permanently closed at one end. A cover engages the central blockto seal the open ends of the perforations and form a multitude ofchambers. A sealing means, operatively associated with the covertogether form a pressure tight seal when a locking means holds cover inengagement with the sealing means to make reaction chambers pressuretight. Applications for the WO 98/36826 invention may, in addition tozeolite synthesis, be in any field of activities within research anddevelopment connected to products where at least one production stepcomprises the mixing of different liquids, e.g., in the fields oforganic and inorganic syntheses, paint production, formulation of fuels,food industry, etc., and, furthermore, applications within clinicaltesting, dissolution and digestion of samples with acid etc. where aliquid reactant is added to a liquid or solid, or a solid is added to aliquid. The invention of WO/9836826 is most useful where open vesselscannot be used, and where it is required to operate at temperatureswhich will cause elevated pressures in the liquid part of the mixture.

The present invention is an advancement in the art as compared toWO/9836826 in that a set of vessels are removably secured withinassociated bores defined by a base. The vessels are constructed ofmaterial that is inert in the reactions or treatments conducted within asynthesis zone including a pressure and temperature conditions as mayoccur when using and substrate or base in any form from simple plate toa multiautoclave. The vessels, being each a single unit, line theinterior of the bores, both the interior walls and one end. The vesselsallow for a simple means of extracting material from the multiautoclaveand can then be replaced with fresh vessels to minimize crosscontamination between runs using the vessels. Optionally, the vesselsmay be used in the weighing of reagents such as powders and liquids forincreased accuracy. Others have employed a liner in specific singlevessel units such as U.S. Pat. No. 4,554,136 A where a fluoropolymerlining is used to inhibit acid corrosion of the walls of the pressurevessel, U.S. Pat. No. 3,048,481 A which discloses a refractory liningused within a synthesis gas generator, and U.S. Pat. No. 3,396,865 Awhich teaches a synthesis pressure vessel having a thermally conductivepressure shell and a chemically resistant thermally insulating liningwithin the shell made of a dense refractory concrete. The presentinvention, however, is unique in its use of a set of vessels tofacilitate solid product removal and minimize cross contaminationbetween runs using the array of vessels.

SUMMARY OF THE INVENTION

The invention allows the making of arrays of materials in quantitiessuitable for research and development using vessels that are easilymaintained in array during the experimentation steps and may bediscarded the array once the experimentation is completed. The inventionovercomes the problems of using a plurality of small vessels in a methodor apparatus where the problems of adequately securing the vessels formanipulation during experimentation while also removing stuck vesselsfrom the array are both overcome. In one form the invention introduces acomponent of a first material into one independent vessel through anopening in its top of the first vessel and introduces another componentof a second material into a different independent vessel through itstop. Both vessels are removably located about a base at different firstlocations. Transformation of the components in the vessels then occursto produce different materials therein. After completion of theexperiments a displacement medium simultaneously urges the vessels fromtheir respective locations about the base for discard or reuse after anynecessary cleaning. Typically at least one property of the materialsfrom the vessels is determined either within the vessel or afterrecovery of the materials.

It is also possible to practice the invention without the use of a baseper se by again introducing the component of first and second materialsindependent vessels. In this case one of the independent vessels isremovably located about one opening in a framework at a one location andanother of the independent vessels is removably located about anotheropening in the framework at a different location. The vessel andframework locations permit contact by the framework with a portion ofeach vessel. In this form the invention also provides a unique trappingsurface for contact with a different portion of each of the vessels whenin their framework locations. Urging the trapping surfaces in unisoninto contact with the vessels create trapping contact between thevessels and the framework thereby fixing the location of the vesselsrelative to the framework for the manipulation of the arrays during thesteps of experimentation. The components in the vessels are transformedto produce materials for experimentation in the desired array using oneor more steps. After the steps, urging the first and second trappingsurfaces out of contact with the first and second vessels permit readywithdrawal of the first and second vessels from the framework. In mostcases the framework will comprise provided a base with bores forreceiving the vessels but the framework may simply comprise an grid ofopenings through which the vessels pass in part.

In another form the invention provides a method of making an array ofmaterials by introducing at least one component of a first material intoa first vessel; introducing at least one component of a second materialinto a second vessel; and removably securing said first vessel at firstlocation within a first bore defined by a base and removably securingsaid second vessel at second location within a second bore defined bythe base by interaction between a surface of each vessel and a wall ofits respective bore. The components in the first vessel are transformedinto the first material and the components in the second vessel aretransformed into the second material. At least a portion of the firstmaterial is recovered in isolation from the second material. In oneembodiment of the invention, at least the first vessel is tapered toprovide the interaction between only a portion of an outer sidewall ofthe first vessel and the inner wall of the first bore. In a more limitedembodiment of this form, at least a plurality of the bores extendcompletely through the base, each bore retains a vessel and theplurality of bores are closed at their distal ends to at leasttemporarily create a pocket by affixing a bottom closure to the basethat covers the distal ends of the bores and optionally removing thebottom closure permits at least partial displacement of the vesselsthrough either side of the bore that removably secures it. Optionallythis embodiment of the invention, may provide a displacement medium inthe form of a series of displacement pins affixed in pattern that alignsa pin with each distal end of the plurality of bores. After the removalof the bottom closure the pins displace the vessels from the bores bycontact of an individual pin with a bottom of each displaced vessel asthe pins are urged into the bores.

The invention can also comprise a unit containing a multitude ofpressure vessels, also referred to as a multiautoclave. Themultiautoclave has typically from 10 to 10,000 or more small, separatechambers that retain a vessel, each typically with a volume of from0.001 to 10 ml. The multiautoclave may be composed of a base havingbores that define the chambers and optionally extend completely throughthe base. Where the bores extend partially through the base a singleplate will cover the top to maintain pressure within the vessels. Whenthe bores extend completely through the base a set of plates will coveropposite faces of the base. Each vessel is removably secured within abore of the base and optionally a thin laminate may be sandwichedbetween the base and either plate to improve the pressure seal.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a base with bores.

FIG. 2 is a plan view of the base of FIGS. 1 and 2.

FIG. 3 is a section of the base of FIG. 2 taken along section 3-3.

FIG. 4 is perspective view of the underside of the base of FIGS. 1-3.

FIG. 5 is a perspective view of a vessel for use in this invention.

FIG. 6 is a front view of the vessel of FIG. 5.

FIG. 7 is an optional cap for sealing the vessel of FIGS. 5 and 6.

FIG. 8 is a front view section of the cap of FIG. 8.

FIG. 9 is a perspective view showing the base of FIGS. 1-4 retaining aplurality of the vessels of FIGS. 5-8.

FIG. 10 is a perspective view of an optional lid for sealing the vesseland base assembly of FIG. 9.

FIG. 11 is a perspective view of the assembled base and lid of FIGS. 9and 10.

FIG. 12 is a sectional view of a base showing different vessel andoptional lid configurations for use with the invention.

FIG. 13 is a perspective view of a displacement medium comprising a jigand aligned pins.

FIG. 14 is perspective view of an alternate base configuration havingshallow bores.

FIG. 15 is section representative of the base of FIG. 14 having vesselstherein and an optional lid configuration.

FIG. 16 is a section showing an alternate arrangement for the basesection of FIG. 15.

FIG. 17 is a section of alternate base, vessel and lid configuration.

FIG. 18 is a perspective view showing an assembly of a framework andwith trapping surfaces to retain vessels and effect their simultaneouswithdrawal.

FIG. 18 a is a perspective view of the framework of FIG. 18 isolatedfrom the assembly of FIG. 18.

FIG. 18 b is a perspective view of the trapping surfaces of FIG. 18isolated from the assembly of FIG. 18.

FIG. 18 c is a perspective view of the framework of FIG. 18 isolatedfrom the assembly of FIG. 18 and retaining vessels.

FIG. 19 is section representative of FIG. 18 with the trapping surfacesin a first position relative to the framework.

FIG. 20 shows the trapping surfaces of FIG. 19 in a second positionrelative to the framework.

DETAILED DESCRIPTION OF THE INVENTION

As summarized above, the invention is a method of making an array ofmaterials. The method uses at least a first and second vessel. Thevessels are described below in greater detail. It is preferred that agreater number of vessels be used in order to enhance the efficiency ofthe method. Eight, sixteen, forty-eight, ninety-six, or a greater numberof vessels may be used. The number of vessels may extend into thehundreds, thousands, or ten of thousands. The vessels are removablylocated about a base or framework.

FIG. 1 shows a perspective view of one embodiment of a base. The base 22defines a multitude of bores having openings 24 in the top of the basefor receiving vessels. When the base is to be used at temperatures inthe range of from about 150 to about 250° C., the base may be made fromstainless steel, aluminum, titanium or other rigid material such aspolyethylethylketone (PEEK) or the like. For use at temperatures above150° C., the base 22 can be made entirely of Teflon™, for use below 130°C. it can be made of polypropylene, and for use below 105° C. it can bemade of polyethylene. It is preferred that the bores be through-going,or in other words, the bores extend from one surface of the base to aparallel second surface of the base. However, as can be seen in FIG. 2the openings 24 of the bore define a passage through the thickness ofbase 22, but only a smaller diameter port 26 to the bottom of base 22.Port 26 provides one form of release opening for use with a displacementmedium as hereinafter described. The difference in the diameter of theopenings of the bores 24 and the ports 26 are shown in FIG. 3 as well asthe depth of the opening 24 through the thickness of base 22. FIG. 4shows port 26 opening in the bottom of base 22. Alternatively, the boresmay define cavities that do not have an opening extending completelythrough the base. In general, the invention will be described below asthe preferred embodiment of a base having bores with bore openings onone surface of the base and ports connecting the bore openings toanother side of the base.

FIG. 5 is a perspective view looking into a typical vessel 28 thatoccupies at least a portion of the bores in the base. The vessels mayconform to the shape of the bores of the base and are positioned so thatan individual vessel extends into at least one of the bore openings 24.FIGS. 5 and 6 show a cylindrically shaped vessel 28. FIG. 6 shows theoutline of the interior of vessel 28 and an optional removed dimple 32from the bottom of the vessel to aid in withdrawal of the vessel. Theindividual vessel lines at least a portion of the walls of the boreopening 24 and lines the bottom of the bore opening near port 26.Alternate vessels are possible and are discussed in more detail below.The vessel is preferably made of an inert polymer material such asTeflon™, polyethylene, polypropylene, perfluoroalcoxy fluorinatedethylene propylene, and polyethylethylketone, that is able to withstandthe temperatures and pressures necessary for synthetic reactions. Thevessels may be constructed of material that is transparent to radiationfor ease of later analysis, such as transparent to infrared radiation ortransparent to x-rays. However, the vessels themselves may provide aconvenient way to provide catalyst function to the reaction occurringwithin the vessel. For example, catalyst may be present on the interiorsurface of the vessels, may be released from cavities within the wallsof the vessels, may be released from an adsorbent that coats the wallsof the vessels, and the like.

In one embodiment of the invention, materials are made in quantitiessuitable for research and development experiments. For example, materialmay be made in quantities ranging from milligrams to grams. The vesselsin this application may have a maximum inner diameter of about 10 mm.Multiple vessels are used in an application, and typically, 8, 48, 96,188 or more vessels are removably located about a base.

The vessels provide several advantages over previous equipment with themost important being the simple means of removing the vessel from thebase. This allowed for a greater degree of flexibility in that differentvessels may be grouped for different types of experiments. Anotherbenefit is the ease of extracting solid products from the separatereaction vessels as compared to extracting multiple solid products froma unitary device. Yet another advantage is the significantly reducedchance of cross contamination between runs using the multiple pressurevessels. Small vessels may improve operations by eliminating the need toclean small confined regions on plates and thereby eliminating the riskof undetected contamination compromising future experiments. Theindividual vessel may also be used to weigh the reagents and or productsto a high degree of accuracy. The vessels may also provide analternative approach to product recovery through using ports 26 in thebase 22. Vessels containing synthesis products may be pressed out of thebores of the base using an extraction device which is discussed ingreater detail below.

At least one component of a first material is introduced into a firstindependent vessel, and at least one component of a second material isintroduced into a second vessel. The components may be introducedserially to each of the vessels, or simultaneously to the respectivevessels. Additional components may also be added to one or more of thevessels. Multiple components may be mixed together and added to avessel, or may be introduced to the vessel separately. When multiplecomponents are each introduced to a single vessel separately, themultiple components may be introduced sequentially or simultaneously.The same or differing amounts of components may be introduced to thevessels. The materials may be inorganic or organic. Preferred materialsinclude zeolites, ceramics, composite materials and the like. The termdifferent materials is meant to include materials produced from the samecomponents. For example, varying the amounts of the components or theorder of addition of the components, although the identity of thereactants remains the same, may results in different product materials.

Various different techniques may be used to introduce the components tothe vessels, such as manual methods and automatic methods. Thecomponents are preferably introduced to the vessels in measured amounts,the measuring may be contemporaneous with the introduction, before theintroduction, or after the introduction. One embodiment may use adispenser such as a pipette, micropipette, or a powder doser. It ispreferred that the dispenser be automatic, but is not necessary.

The components are transformed, while in the vessels, into materialshaving at least one property that is different from that of the startingcomponent. It is expected that the transformed materials between atleast two of the vessels would have at least one property that isdifferent.

FIGS. 7 and 8 show an optional lid that may cover the top of the vessel.FIG. 7 shows the outline of an hollowed portion 36 on the interior of alid 34. Lid 34 may be inserted into the opening of interior portion 30of vessel 28. Lid 34 may be shaped with a tapered end 33 to facilitatethe insertion of lid 34 into interior portion 30 of vessel 28. Lid 34may also have top portion 35 to prevent lid 34 from completely insertingwithin interior portion 30 of vessel 28. One purpose of lid 34 is toretain the components and materials within the vessel during handling,processing, and transformation. Another purpose of lid 34 is to provideclosure of the vessel for purposes of maintaining an internal pressuresuch as that required for hydrothermal synthesis. Lid 34 may beconstructed of materials as described for the vessel and the base above.

FIG. 9 shows a plurality of vessels 28 and lids 34 assembled into a base22. and FIG. 10 shows a retaining plate 38 that contacts the lids tourge the bottom of vessels 28 into contact with the bottom of therespective bores in base 22 when assembled with the base of FIG. 9 intothe assembly shown in FIG. 11. Retaining plate 38 may also operated tourge a portion of lid 34 into the interior portion of vessel 28. Thelids may actually be an integral part of the retaining plate, or theretaining plate may retain a separate lid for each vessel that has alid. The vessels 28 are removably placed within bore openings 24 definedby base 22. The vessels may be removably placed about the base before,during, or after the components have been introduced. The vessels may beremovably placed about the base sequentially, at the same time, or ingroups. In one embodiment, a bore contains no more than one vessel. Theterm about a base is meant to include within, on, or against the base.

Optionally, retaining plate 38 may be fixed to base 22 using clamps orfasteners. Threaded fasteners may operate through bores in retainingplate 38 and corresponding bores in base 22 to maintain the assemblyduring handling and processing.

The retaining plate serves several functions. The retaining plate incombination with the lids provide for a mechanism for independentlysealing each of the vessels in order to retain materials within thevessels during mixing operations such as shaking, vibrating, stirring,tumbling, and the like. Furthermore, with each vessel beingindependently sealed, the components within a vessel may be mixedwithout resulting in cross contamination between different vessels. Onepossible feature of the invention employing one or more retaining platesis that a large number of assemblies may be placed on top of each otherforming layers of reaction chambers according to the desired capacity.As an example, ten assemblies as shown in FIG. 11 can be placed on topof each other. The retaining plate, or the lid, or the combination ofthe retaining plate and the lid may also operate to provide pressurethat prevents the vessels from rotational movement with respect to thebase, or the retaining plate may operate to prevent the vessels from anymovement with respect to the base.

FIG. 17 more completely illustrates the use of fasteners in the form ofbolts 48 that extend through a hole 52 in a top retaining plate 38′, ahole 54 in a base 58 that defines through going bores 60 and a hole 56in a bottom retaining plate 46. The bolts 48 engage nuts 50 to securethe whole assembly together once vessels 62 are ready for sealing. Tofacilitate work with the vessels before closing retaining plate 38′optional bolts 64 may pass through holes 66 and engage a threaded hole68 in base 58 to secure it to the base while moving the open ends ofvessels 62 in base 58 to the various locations required for theexperimentation steps.

The invention is suitable for use with a wide variety of base, retainingplate and vessel configurations. FIG. 17 also demonstrates the use ofvessels 62 having lips 70 that extend radially outward over the top ofbase 58. These lips have a thickness much less than the depth of vessels62. Securing retaining plate 38′ to base 58 will squeeze lips 70 betweenthe two contacting surfaces to provide the necessary seal to maintainpressure in vessels 62. Preferably the bolts 48 and nuts 50 are placedin such a manner and their number adjusted so that a sufficientlydistributed even load is obtained in order to ensure that all thechambers are tight when in use. Additionally the squeezing mechanism mayinclude springs or the like, which ensures the maintenance of a suitablepressure. A frame made of a rigid material that ensures good tightnessin the outer chambers may enclose the entire assembly, alsocounteracting deformation of plates made of pure Teflon™ or anotherductile material.

FIG. 12 further shows the variety of vessels that can occupy the boresand use the retaining plate as shown in FIGS. 3 and 17. At the locationof each vessel 28 base 22′ further defines ports 26. Retaining plate 38′retains lids 34 in various forms as described. Vessels 28 a have taperedgeometries where a closed end has a diameter less than that of an openend and vessels 28 a and are completely contained within the bores ofbase 22′ with the exterior surface of the open end of the vessel beingin contact with the surface of the bore. Many closure arrangements canseal the tops of vessels 28 a for retaining pressure. In its simplestform the underside of retaining plate 38″ may provide sufficientcontainment contacting the proximate face of base 22′ with enough forceto seal the bore that retains vessel 28 a. Placing a gasket or otherthin layer of sealing material between the two contact surfaces of base22′ and retaining plate 38″ can increase the effectiveness of the sealacross the bores that retain vessels 28 a. Retaining plate 38″ may alsoprovide a direct seal with the top of vessel 28 a using a lid 34′integrated into retaining plate 38′ and extending below its bottomsurface such that the bottom of lid 34′ directly contacts the rim ofvessel 28 a.

Vessels 28 b also have tapered geometries where a closed end has adiameter less than that of an open end. Vessels 28 b, while positionedwithin the bore, extend beyond the opening of the bore in the base. Theportion of vessels 28 b that extend beyond the bore 28 b provide aprotruding region of the vessel having an enlarged outer diameter withrespect to the diameter of the bore The exterior surface of vessels 28 bare in contact with the bore opening and adaptation of such contact intoa suitable force-fit within the bores allows frictional forces tooperate against rotation or other movement such as translationalmovement of the vessels during the steps of experimentation. However,the retaining plate and or lids may also be used to prevent crosscontamination or to contain materials within the vessel during mixing.All of vessel 28 c, 28 d, 28 e and 28 f have a cylindrical geometry.Vessels 28 c, 28 d, and 28F while positioned within the bore, all extendbeyond the opening of the bore in the base. Retaining plate 38″ maycontact the tops of any or all of these vessels to prevent theirmovement within bore and if desired provide a pressure seal between therim of the vessels and the underside of retaining plate 38″. Althoughnot required, any of the cylindrical vessels may be force-fit within thebores as described above for the tapered vessels in order to restrictagainst rotation or other movement. For example Vessel 28c may undergo aslight force-fit with the base 22′ when inserted in a bore to maintainits position. Vessel 28d may fit relatively loosely into its respectivebore and relies on contact with surface of retaining plate 38″ to keepit positioned within base 22′. Vessel 28 f is a two-piece vesselcomprised of a bottom disk 72 in combination with a detachable side wallin the form of a sleeve 74. The sleeve 74 rests on an at least partiallyclosed bottom 76 of the bore. Pressure from retaining plate 38″ againstthe top of sleeve 74 urges it into contact with disk 72 so that sidewallsection and bottom section function as a unitary vessel while optionallyprovided a seal at the top of sleeve 74 with the underside of retainingplate 38″.

As with the unitary vessels, vessel 28 f may be contained within thebore, or may extend beyond the bore as shown. As depicted the bore ofbase 22′ completely contains vessel 28 e such that adjacent lid 14′ ispartially inserted within the bore to contact the rim of vessel 28 e.

Using any vessels, force-fitting of vessels, addition of components tovessels, deformation of vessels undergoing sealing, exposure to pressureand temperature conditions under experimentation, and other procedureswill create the need to extract the vessels from the base. Vesselslodged within a bore may be extracted from the base using a displacementmedium. One form of such a medium is an extraction tool such as thatshown in FIG. 13. Extraction tool 40 has a jig 44 for positioning pins42 in alignment with ports 26 of the bores or through going bores 60 inorder to disengage the vessels from the bores. Extraction tool 40provides for simultaneous disengagement of the vessels from the bores.In one embodiment of the invention, extraction occurs by placing a baseof the type shown in FIGS. 1-4 or 17 that contains vessels 28 or 62within the bores over the extraction tool and forcing it downward sothat pins 22 enter either the open bore or ports 26 and contact vessels62 and 28. Continued force would result in disengagement of the vesselsfrom the bores of the base.

Many alternate forms of a displacement medium for removing more than onevessel at a time from the bores are within the scope of the invention.For example, another form of mechanical displacement medium couldmanually mechanically seize at least a portion of several vessel about asurface of each vessel to withdraw the seized vessel from its bore. Ifthe vessel is formed of relatively soft material such extractor coulduse an array of hooks or puncturing devices to penetrate an interior orexterior surface of individual vessels as moves toward the block andthen simultaneously remove the engaged vessels as it is withdrawn. Otherforms of mechanical displacement mediums may engage a lip, tab othermember on the vessel to withdraw it from the base. For instance a seriesof thin members may slide under the lip 70 of the vessels as shown inFIG. 17. In one form such a removal device can simply comprise anextractor in the form of a flat plate with enlarged openings that fitaround the outer edges of lips 70 and of suitable thinness to slideunder the lips 70 when urged against them for lifting of the vesselsfrom the base with the plate. Such a surface fluidic or electromechanical displacement medium may also find use in this invention. Forexample with the use of ferrous vessels a magnetic field may provide thedisplacement medium to attract or repel the vessels from a block. Moresimply the displacement medium can comprise a compressed gas such as airdelivered to one side of through going bores 60 or ports 26. An openchamber sealed around the bottom perimeter of a block 22 may deliver theair. Alternately, an additional block 22 in the form of that shown inFIG. 4 may serve as manifold which when in bottom side to bottom sidecontact with a similar block 22 delivers compressed gas out of its ports26 and into corresponding ports 26 of the similar block to blow thevessels from the bores that retain them. Similarly the a block 22 canserve as a vacuum manifold by placing its bottom over the top of asimilar block 22 that retains vessels and drawing a vacuum between theindividual vessels and the ports 26 as the two block are maintained inat least partially sealed contact. Drawing the vacuum can either merelydislodge the vessels extraction by an additional displacement medium ormaintaining the vacuum between individual vessels and ports 26 may allowcomplete withdrawal of the vessels with removal of the block 22. Thusthe displacement medium can comprise any effective force delivered tothe vessels to effect displacement of withdrawal of more than one vesselat a time.

The array of vessels need not extend significantly into a bore or into abore at all to utilize this invention. FIGS. 14-16 illustrate shallowdepressions 80 with optional holes 82 or simply holes 84 on differentregions of base 78. Depressions 80 and holes 84 can retain the vessels86 or 86′ (shown in outline) in place on the regions. The size of holes80 may permit a force fit with the outside wall of vessel 86 to retainthe vessels on the plate. Blowing compresses gas through the optionalholes 82 can again serve as a displacement medium to eject the vessels86 from depressions 80. Alternately placing vessels 86 with a relativelyloose fit into the depressions 80 and then drawing and maintaining avacuum through the optional holes 82 can provide the retaining force forthe vessels. In such an arrangement releasing the vacuum through holes82 also releases the vessels such that the absence of the vacuum servesas the displacement medium. The use of the vacuum displacement mediumcan eliminate the need for depression 80 altogether where sufficientretention is possible by merely drawing the vacuum through holes 84 tocreate enough force to retain vessel 86′ directly on the surface of base78.

To use another form of displacement medium the vessels 86 or 86′ cancomprise a ferrous material and the area of holes 82 or 84 can serve aspoint contacts in an array of electro-magnets that can contain vessels86 or 86′ on the base until release of the vessels by de-energizing themagnets. In another embodiment base 78 can comprise one largeelectromagnet for retaining ferrous vessels that thereby eliminates theneed for any holes or depressions.

FIG. 15 shows a section that further illustrates all of the foregoingdescription of the vessel and base interaction along with additionalforms of displacement mediums. On the far right FIG. 15 shows a vessel86′ retained on the top of the base 78 by connection with a source ofvacuum through hole 84. Next, to the left in FIG. 15 a vessel 86 residesin a depression 80. Again vessel 86 may have a force-fit with depression80 in which case hole 82 can accommodate a mechanical or pneumaticdisplacement medium to force vessel 86 and several similarly situatedvessel from depression 80 when desired. Alternately vessel 86 may fitrelatively loosely into depressions 80′ not having optional hole 82retains vessels 80 in a force fit as previously described and hole 86may retain the vessel 86 selectively in place through vacuum or othermeans. An offset retaining plate 90 contacts the top of the vessels 86and retains them in depressions 92. Securing offset retaining plate 90by threading bolt 94 into threaded hole 96 of base 78 providesadditionally stability to the base and vessel assembly for transportvessels and/or agitation of the materials contained therein and can alsoprovide sealing of the vessels for pressure operations. Retaining plate90 in combination with the depressions 92 may provide another form ofmechanical displacement medium when unbolted from base 78 by using theplate 90 to simultaneously tip two or more of vessels out of depressions80′ thereby eliminating the need for any other displacement medium.

In a similar manner to that just described it is also possible to usethe same displacement medium for removing relatively rigid vessels froma relatively pliant and preferably elastic base wherein the base permitsmost of any necessary deformation to retain the vessels in a force-fit.Release of the vessels, in this instance while possible using many ofthe different displacement mediums as already described, may againsimply rely on engagement and tipping of the vessels from the base usinga grid for simultaneous contact of the vessels. A framework 120 ortrapping plate 108 as later described are examples of such grids thatcan engage the tops of the vessels for tipping from the base.

Retaining plate 90 may also include ports 98 for communicating fluidswith the vessels 86. A plenum 100 brazed or welded in place over the topof retaining plate 90 can provide a sealed chamber 102 for communicatingor evacuating fluids from vessels 86. By pulling a vacuum in the chamber102 retaining plate can serve as a vacuum for of displacement mediumthat permits simultaneous lifting of the vessels 86 from the depressions80′. The chamber 102 can also deliver fluids for treatment or testing ofthe materials in the vessels 86. Plenum may be divided as withindividual piping to each divided area to provide any number ofdifferent fluids to groups of vessels 86 or even individual vessels 86.

FIG. 16 provides another alternate arrangement for situating vessels 86″directly on the top of the base 78. Vessel 86″ have posts 88 dependingform their bottoms for insertion into hole 84 that extends completelythrough base 78 or hole 84′ that extends partially into the base. Post88 may engage holes 84 or 84′ in a force fit or a loose fit for ejectionof the post by mechanical pneumatic or other displacement medium in thecase of a force-fit and retention by vacuum, magnetic or other retentionmethods susceptible to selective de-energizing. Again a retaining plate90′ may secure the vessels more firmly to the base by use of a bolt 94and a threaded hole 96. The addition of guide plate 104 for engagementwith the sides of base 78 can further improve stability enhancingfunction of retaining plate 90. Retaining plate 90′ in combination withstubs 106 that depend from its underside into vessels 86″ can provideanother form of mechanical displacement medium when unbolted from base78 by using the plate 90′ to simultaneously tip the posts from two ormore of vessels out of holes 84 or 84′. Retaining plate 90′ may alsoinclude ports 98′ for communicating fluids or solids with the vessels 86and may again use a plenum in communication with the ports 98′.

FIGS. 18, 18 a, 18 b, and 18 c illustrate another embodiment of theinvention that uses the release of a mechanical retaining device toprovide the displacement medium. FIG. 18 shows an assembly 126 of a trapplate 108 having trapping surfaces in the form of holes 112 positionedover a framework 110 for movement of the trapping surfaces in unison. Asshown in FIG. 18 a framework 110 comprises an array holes 116 in a flatplate 118 supported by sidewalls 120. FIG. 18 c show vessel 114′occupying all of the holes in the 116 in framework 110. Holes 116 have aloose fit for contact with a portion of the sidewalls of the vessels.The size of the holes permits their ready insertion and withdrawal fromframework 110. Framework 110 can have a hollow interior as depicted inFIG. 18 a or may comprise a solid block with bores that extend partiallyor completely through the base. Ordinarily framework 110 will have abottom plate to prevent the vessel from dropping completely throughholes 116. To complete the assembly plate 108 rests on top of framework110 and vessels 114′ extend through holes 112 that are sized to fitreadily over the vessels for contact with a portion of the vesselsidewalls.

FIGS. 19 and 20 show the relative positioning of framework 110 andtrapping plate 108 during for the retention and release of the vessels114′. FIG. 119 shows the release position where the holes 122 oftrapping plate 108 align in a relatively concentric manner with respectto holes 116 of framework 110 to permit ready insertion and withdrawalof vessels 114′. Positioning framework 110 and plate 108 in this mannerallows insertion of the vessels 114′ into assembly 126 individually orcollectively through holes 122 and 116. As the vessels 114′ are droppedinto the assembly they rest on an optional retaining plate. Simultaneouswithdrawal of multiple vessels 114′ from the assembly 126 is effected byeither withdrawing the bottom plate 124 or lifting the assembly 126 toleave the vessels 114′ on the bottom plate 124. The effectiveness of thepinching action of plate 108 and framework 110 in retaining vessels 114′allows enlarging sizing of holes 122 and 116 that eliminates adhering orsticking of the vessels 114′ within assembly 126 when it is positionedfor release of the vessels as shown in FIG. 19.

After insertion of the vessels 114′ into the assembly as shown in FIG.19, positioning plate 108 and framework 110 in the relative positionsshown in FIG. 20 will retain the vessels in the assembly 120 for movingof the vessels during the different steps of experimentation. Withvessel 114′ in place, sliding plate 108 to align holes 122 in aneccentric arrangement relative to holes 116 causes trapping surfacesprovided by edges of holes 116 to simultaneously contact portions of thevessel 114′ on one side while on the opposite sides of the vesselsopposing trapping surfaces provided by edges of a holes 122 whilesimultaneously contact portions of the vessels on an opposite and at aslightly higher point on the vessels. The assembly can employ anysuitable clamp detent to hold the relative positions of plate 108 andframework 110 in the trapping position until the desired release orremoval of vessels 114′ from the array.

The steps used in the transformation of the component or componentscontained by the vessels may be any of those commonly known in the art.Heat may be applied, stirring, mixing, agitation, hydrothermalconditions, and the like. Multiple steps may be employed, or a singlestep may be used, for example, it is often desirable to calcineinorganic samples after synthesis. Washing, grinding, and sieving areadditional optional steps. Different components may be added betweentransformation steps. The materials formed may be further process oranalyzed using different techniques and are not required to be treatedas an array. The materials are retained in the defined matrix that, in asimple manner, can be transferred to an automatic sample-switching unitfor analysis, e.g., by X-ray diffraction or IR thermography.

An added advantage of using the independent vessels is that the base isready to be used again with no or only minimal cleaning. Residue fromthe previous reactions is removed in the vessels and the base isvirtually residue-free for subsequent synthesis reactions. The overallbenefits of the advances in the present invention are primarily relatedto the increase in efficiency in removing the synthesized materials, thereduction in cross contamination, and the increase in efficiency inpreparing the apparatus for subsequent use. Advances in the automatedlayout will make it possible to more efficiently perform large numbersof syntheses/formulations simultaneously, and it will thus be veryuseful for all research laboratories in industry as well as in researchinstitutions/universities.

1. A method of making an array of materials in quantities suitable forresearch and development experiments comprising: a) introducing at leastone component of a first material into an independent first vesselthrough a top opening of the first vessel; b) introducing at least onecomponent of a second material into an independent second vessel througha top opening of the second vessel; c) removably locating theindependent first vessel about a first opening in a framework at a firstlocation for contact of a first portion of the vessel with the frameworkand removably locating the independent second vessel about a secondopening in the framework at a second location for contact of firstportion of the second vessel with the framework; d) positioning a firsttrapping surface for contact with a second portion of the first vesselwhen the first vessel is located in the framework and a second trappingsurface for contact with a second portion of the second vessel when thesecond vessel is located in the framework; e) urging the first andsecond trapping surfaces in unison into contact with the first andsecond vessels to create trapping contact between the first and secondvessels and the framework thereby fixing the location of the first andsecond vessels relative to the framework; and, f) urging the first andsecond trapping surfaces out of contact with the first and secondvessels to permit withdrawal of the first and second vessels from theframework.
 2. The method of claim 1 wherein the framework is provided bya base and the base defines bores that retain the vessels and a least aportion of the bore provides the first trapping surface.
 3. The methodof claim 1 wherein the first and second trapping surfaces move inopposite directions along parallel paths to engage the vessels.
 4. Themethod of claim 2 wherein the second trapping surface comprises aretaining plate that covers the open end of the vessels, clamping of theretaining plate over the base engages the plurality of vessels andoptionally the tops of the vessels extend above the bores and pressurefrom the retaining plate seals the interior of the vessels.